Consolidation of formations by electroless metal plating process

ABSTRACT

THE METHOD OF CONSOLIDATING INCOMPETENT FORMATIONS AT LOW TEMPERATURES IN THE PRESENCE OF AN ELECTROLESS BASIC METAL PLATING SOLUTION UNDER CONDITIONS OF REDUCED STRESS BY ADDITION TO THE SOLUTION OF A SMALL AMOUNT OF AN ORGANIC SULFIMIDE.

3,586,524 Patented June 22, 1971 ABSTRACT OF THE DISCLOSURE The method of consolidating incompetent formations at low temperatures in the presence of an electroless basic metal plating solution under conditions of reduced stress by addition to the solution of a small amount of an organic sulfimide.

BACKGROUND OF THE INVENTION Inthe U.S. Pats. 3,393,737; 3,438,440; 3,438,441 and pending applications Ser. No. 692,726 filed Dec. 27, 1967 which matured into US. Pat. 3,500,926 and Ser. No. 705,- 907 filed Feb. 16, 1968 which matured into U.S. Pat. 3,500,927 electroless metal plating techniques are described for consolidating unconsolidated formations and it is disclosed that the process provides advantages rela tive to resin consolidation techniques for consolidating earth formations as described in such papers as J. Pet. Tech. May 1966, p. 545 entitled Review of Sand Consolidation Experience in Southern Louisiana I. L. Rike, or I. Pet. Tech. December 1961 paper entitled Large-Scale Laboratory Investigation of Sand Consolidation Techniques by W. F. Hoover, or I. Pet. Tech, December l966, p. 1537 article entitled Studies of a New Process to Consolidate Oil Sands With Plastics by B. R. Treadway or as described in U.S. P-ats. 3,412,796; 3,419,072; 3,378,071; 3,373,813; 3,310,111; 3,282,338 and the like. In essentially all of these resin consolidation processes for consolidating incompetent formations rigs are required and curing time is difficult to control the resin coating or binding materials are difficult to control relative to temperature changes encountered in the treated formation and these materials also present a water stability problem and are aifected by the presence of corrosive acids and the like. This often results in costly operations'of restrictive use and benefit and therefore makes the electrolesslmetal consolidation techniques described in the above-mentioned references more attractive since metal consolidated formations require no rig, the formations thus treated are not alfected by temperature changes and are water stable and impart high compressive strength to such metallized consolidated formations.

Under low temperature conditionsas described in U.S. Pat. 3,43 8,441, wherein basic electroless metal plating solutions are used to consolidate formations, realitively high plating reaction rates may result in consolidated formations which have a low resistance to stress and are subject to cracking. In this case, whenv such formations are contacted with hot fluids formation damage results.

It has now been discovered that the addition of a small amount of metal plating solution results in controlled metal deposition and consolidation of formations which are resistant to stress and hot fiuid damage. Thus, in consolidating sands or coating materials at substantially normal room temperature, excellent uniform metal coatings are produced by using alkaline-plating solutions containing organic sulfimides such as saccharin.

As indicated, a sulfimide such as saccharin is unique in its capability of providing competent metal coatings where alkaline solutions are used at relatively low temperatures.

However, the metal plating of subterranean earth formations may be used to disperse and implant metal to be used as catalysts, activators, property indicators, etc. In the latter operations it may be advantageous to form deposits which crack and expose large surface areas of metal.

The present invention involves the discovery that in an electroless metal plating at a given temperature the degree of competency of the coating is uniquely responsive to the rate of reaction of the plating solution at the given temperature. This discovery is contrary to what would be expected from the effects from strain-reducing additives in electrolytic metal plating. It can be utilized to form highly competent, or incompetent, coatings at the option of the operator, Moderately cracked coatings can be formed by diluting a solution having a relatively high rate of reaction with a solvent such as 2-ethoxyethanol (Cellosolve), dioxane, glycerol, etc. Highly cracked coatings can be formed by diluting such a solution with a lower .alcohol such as isopropanol.

PREFERRED EMBODIMENT OF THE INVENTION The activator solutions can be any of the activator solutions described in U.S. Pats. 3,393,737; 3,438,440 or 3,43 8,441 and include stannous chloride and/ or palladium chloride solutions which may contain hydrazine and which solutions can be buffered with Weak organic acids and their salts. Preferred activator solutions are shown in Tables 1 and 2.

TABLE 1.COMPOSITION OF ACTIVATOR SOLUTION (A Quantity per barrel of solution 1 Nom Chemicals must be added to the water in the order listed with complete mixing and dissolving before adding the next chemical.

1 Contains 10.2 grams PdC12/bb1. of activator solution.

9 Requires about 15 minutes to dissolve.

3 Or 400 cc. of 35% hydrazine.

4 Contains 1.6 gms. PdClz, 10 cc. conc. HCl, 90 cc. distilled or deionized water/100 cc. PdCl2 solution.

TABLE 2.--ACTIVATOR SOLUTIONS (B 900 cc. water 100 cc. of solution comprising 919 cc. water 81 cc. gum arabic solution containing 0.4/gram/1 0.4 cc. hydrazine hydrate (85% solution) 1.0 cc. of a solution containing 1.6 grams PdCl '2H O 10 cc. conc. HCl

cc. water Add glacial acetic acid to give PH=4.2

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H2 cc.

NiC1T6H1O, grams/l 34 8 NiS O4 6H O grams/1- NaHzPOrHzO. grams/1 29.4% NHa, cc./l NHlCl, grams/l Na glycolate, grams/l Na succlnatefiH O grams/ 70% glycolic acid, cc./l NaOH, grams/l 2O,CC-/l 860 860 827 865 805 NiSO4-6HzO,grams/l 42.0 42.0 42.0 43.0 43.0 N tlP02'Hz0,gTamS/1 38.0 38.0 38.0 46.3 46.3 (Nfinzsol, grams/1.- 79.0 79.0 40.0 80.0 80.0 29.4% N113, 05.11.... 52.0 52.0 115 53.0 53.0 SaccharimgramS/L. 10 10 10 8.0

Na Saccharin-2H O, Aisisaccharin, grams/l p H2O, cc./l NiClz-SHzO, grams/l NaHzPOz-HzO, grams NH401, grams/l 29.4% NH ee./l Saccharin, grams/L... pH

1 l0 g./l. Acetic Acid System (see EPR, 114-67-F).

Saccharin also changes the relative importance of side reactions, giving slightly less H production (not noted in Table 4) and more acid production, which lowers the pH in spent solution (see runs 17 and 18). This effect of saccharin on hydrogen production may indicate that saccharin plays a role in the stress-relieving reaction by causing some H+ to form (assumed to be a fast reaction) instead of H gas (assumed to be a slow one) from the chemisorbed H on the metal. Also, this may be the mechanism by which saccharin slows down the overall deposition reaction.

The metal plating process of this invention can be modified by any of the methodsdescribed in the above patents on the subject as well as in copending applications Ser. No. 850,253 filed Aug. 14, 1969 and Ser. No. 835,- 243 filed June 20, 1969 wherein spacer and backflush fluids are employed for this process of consolidating formations.

This invention provides a uniquely advantageous way of avoiding problems encountered in consolidating incompetent subterranean reservoir formations. It is also useful in controlling the competency of substantially any coating deposited by electroless metal plating from an alkaline plating solution on substantially any material. It

is particularly useful where the plating is effected by flowing a plurality of pore volumes of activating and plating solutions through a permeable non-catalytic material, such as a permeable earth formation, a permeable mass and/ or structure of plastic, metal, or the like material that is non-catalytic to such a metal deposition, etc. The plating can be efiected in order to improve the strength or stability ofa granular material and/or an intergranular cementing material within a mass of granular material and/or to plug or reduce the permeability of such a mass or permeable structure, to bond catalytic and/or conductive metal within such a mass or structure, to bond other materials into such a mass or structure, etc.

We claim as our invention:

1. A method of consolidating an incompetent formation comprising treating the formation with an activating solution and thereafter treating the activated formation with a basic metal plating solution containing a small amount of an organic sulfimide until the formation is consolidated into a crack-resistant, water-resistant formation.

2. The method of claim 1 wherein the activating solution is a palladium halide solution and the metal plating solution is a basic nickel halide solution containing saccharin.

3. The method of claim 2 wherein the activating solution is a palladium chloride solution containing a buffering agent and the nickel containing solution is a basic nickel chloride solution. i i

4. The method of claim 3 wherein between the activator and basic metal plating solutions a spacer fluid is injected into the formation. 1

5. A method of depositing metal on a solid material comprising contacting the solid material with an activating solution followed by treating said activated solid material with an electroless basic metal plating solution containing a small amount of an organic sulfimide until metal is deposited on the solid material.

6. The method of claim 5 wherein the solid material is a permeable structure composed of non-catalytic material..

7. The method of claim 5 wherein the activating solution is a palladium halide solution and the metal plating solution is a nickel halide solution containing saccharin.

References Cited UNITED STATES PATENTS OTHER REFERENCES Domnikov, Larissa Electroless Nickel Plating from Alkaline Solutions. In Metal Finishing, March 1966, pp. 57-60.

IAN A. CALVERT, Primary Examiner US. (:1. X.R. roe-1; 117-54; 166-300 

